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EP1242347B1 - Procede de production de phenolates de phosphonium - Google Patents

Procede de production de phenolates de phosphonium Download PDF

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Publication number
EP1242347B1
EP1242347B1 EP00983239A EP00983239A EP1242347B1 EP 1242347 B1 EP1242347 B1 EP 1242347B1 EP 00983239 A EP00983239 A EP 00983239A EP 00983239 A EP00983239 A EP 00983239A EP 1242347 B1 EP1242347 B1 EP 1242347B1
Authority
EP
European Patent Office
Prior art keywords
phosphonium
process according
reaction
phenolates
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00983239A
Other languages
German (de)
English (en)
Other versions
EP1242347A1 (fr
Inventor
Lothar Bunzel
Uwe Hucks
Annett KÖNIG
Silke Kratschmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1242347A1 publication Critical patent/EP1242347A1/fr
Application granted granted Critical
Publication of EP1242347B1 publication Critical patent/EP1242347B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
    • C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds

Definitions

  • the application relates to a process for the preparation of phosphonium phenolates.
  • the object of the present application is therefore to find a process in which the Temperature stress and the amount of solvent obtained as low as possible remain, but the purity of the phosphonium phenolate is as high as possible.
  • the application relates to a process for the preparation of phosphonium phenolates by reacting phosphonium halides and phenols in aqueous alkaline Solution, characterized in that the phosphonium phenolate prepared separated from the synthesis mixture by crystallization.
  • the reaction is preferably carried out at temperatures of 0 to 55 ° C, in particular 15 to 50 ° C performed.
  • the reaction is preferably carried out at molar ratios of phenol to phosphonium halide from 2: 1 to 10: 1, preferably from 4.5: 1 to 6: 1 and in particular 5: 1 performed.
  • the reaction is preferably carried out at pH values from 9.5 to 11, preferably from 9.5 to 10.5 and in particular from 10 to 10.5.
  • the reaction is optionally carried out in the presence of alcohols in amounts of 50% by weight to 200% by weight, preferably from 66% by weight to 125% by weight carried out by weight aqueous phase, the alcohols preferably have a maximum solubility in pure water of 15% by weight.
  • the phosphonium phenolates produced in this way contain no more than 0% by weight. Halide.
  • radicals R 1 to R 4 are each a C 6 -C 14 aryl radical or the radicals R 1 to R 3 are each a C 6 -C 14 aryl radical and R 4 for a C 2 -C 12 alkylene radical.
  • These compounds (I) are formed in the reaction of trialkyl or triaryl phosphines, for example triphenylphosphine with haloarylene or haloalkylene, e.g. Benzyl bromide in the presence of metal salts (Friedel-Crafts alkylation) or in the presence of Grignard compounds and cobalt (II) chloride.
  • trialkyl or triaryl phosphines for example triphenylphosphine with haloarylene or haloalkylene, e.g. Benzyl bromide in the presence of metal salts (Friedel-Crafts alkylation) or in the presence of Grignard compounds and cobalt (II) chloride.
  • Preferred phenols for the reaction are phenol or substituted phenols as well as bisphenols.
  • Phosphonium phenolates of the formula (III) are preferably prepared wherein the radicals R 1 to R 7 and n have the meanings given above.
  • demineralized water or distilled water used for the preparation of the aqueous-alkaline phase.
  • the pH from 9.5 to 11.0 preferably from 9.5 to 10.5, particularly preferred from 10.0 to 10.5, preferably with the aid of an alkali metal hydroxide solution, preferably Sodium hydroxide solution or potassium hydroxide solution - taking into account the buffering effect of Phenol / Na phenolate - discontinued.
  • an alkali metal hydroxide solution preferably Sodium hydroxide solution or potassium hydroxide solution - taking into account the buffering effect of Phenol / Na phenolate - discontinued.
  • the process according to the invention can be carried out continuously or batchwise are, with a batch operation is preferred.
  • phenol, phosphonium halide and Alcohol presented as a solution and water added.
  • the pH value is adjusted to 9.5 to 11.0 with the addition of alkali lye, preferably set from 9.5 to 10.5, particularly preferably from 10.0 to 10.5.
  • This is preferably carried out with intensive mixing of the reaction components Temperature kept from 0 to 55 ° C, preferably 15 to 50 ° C.
  • the response time should be less than 2 hours, preferably less than 1 hour.
  • the phosphonium phenolate produced according to the invention is isolated, preferably by using a water-poorly soluble alcohol (the Solubility of the alcohols in water is known from the literature), the aqueous phase of the separates organic phase and the latter at least 1 times, preferably 3 times with deionized water or distilled water extracted. Then the solution to 26 cooled to 0 ° C, preferably to 23 to 10 ° C. The precipitated phenolate will then suctioned off and cleaned by washing. If necessary, that will product recrystallized and dried.
  • a water-poorly soluble alcohol the Solubility of the alcohols in water is known from the literature
  • Alcohols suitable according to the invention for the reaction solution are aliphatic of the formula C n H 2n + 1 -OH, where n is an integer from 4 to 10 inclusive, such as.
  • Alcohols suitable according to the invention for the reaction solution are also cycloaliphatic of the formula C n H 2n-1 -OH, where n is an integer from 5 to 10 inclusive, such as.
  • alcohols can also be used to wash out the phenolate be used.
  • it can also be used in water soluble alcohols are used, such as.
  • ethanol n-propanol or isopropanol.
  • polyvalent aliphatic or cycloaliphatic Alcohols are used.
  • Preferred aliphatic alcohols are propanols, (iso) butanols, pentanols and Hexanols, especially isobutanol and isopropanol.
  • Preferred cycloaliphatic alcohols are cyclopentanol, cycloheptanol and Cyclooctanol, particularly preferably cyclohexanol.
  • the weight ratio of water to alcohol is between 2: 1 and 1: 2, preferably between 1: 1 and 1: 2.
  • the alcohols to be used according to the invention are used for better workup added because the phenol / alcohol mixture has a lower density than the aqueous one Has solution and is thus the organic over the aqueous phase.
  • the aqueous phase to be drained below, the organic phase containing the phenolate contains, can then be washed in the same separation vessel with demineralized water and that Wash water in turn can be drained below.
  • Quaternary phosphonium phenolates produced according to the invention are in particular the compounds of the formulas and
  • the phosphonium phenolates produced in this way are particularly suitable as catalysts for esterification and transesterification, especially for the production of polycarbonates according to the melt transesterification process (see US 3,442,854).
  • the melt transesterification process is known to start from aromatic, for example Diphenols, carbonic acid diaryl esters and optionally branching agents and / or monophenols.
  • the phosphonium phenolates obtainable according to the invention are used as catalysts in amounts of 10 -1 mol to 10 -8 mol, preferably in amounts of 10 -3 mol to 10 -7 mol, per mol of diphenol.
  • melt transesterification process is described in the literature (see for example Hermann Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, 1964, pages 44 to 51, DE-A-1 031 512, U.S. 3,022,272, U.S. 5,340,905 and U.S. 5,399,659).
  • Thermoplastic polycarbonates are solvent-free and have a light color of their own and largely free of undesirable defects in the polycarbonate.
  • thermoplastic Polycarbonates for example in electrical engineering, as lamp covers, as security disks or as optical data storage such as CD material.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (8)

  1. Procédé de préparation de phénolates de phosphonium par mise en réaction d'halogénures de phosphonium et de phénols dans une solution alcaline aqueuse, caractérisé en ce que l'on sépare le phénolate de phosphonium produit par cristallisation à partir du mélange de synthèse.
  2. Procédé selon la revendication 1, caractérisé en ce que la mise en réaction est réalisée à des températures de 0 à 55°C.
  3. Procédé selon au moins une des revendications 1 ou 2, caractérisé en ce que la mise en réaction est effectuée à des rapports molaires du phénol à l'halogénure de phosphonium de 2:1 à 10:1.
  4. Procédé selon au moins une des revendications 1 à 3, caractérisé en ce que la mise en réaction est effectuée à des pH de 9,5 à 11.
  5. Procédé selon au moins une des revendications 1 à 4, caractérisé en ce que la mise en réaction est effectuée en présence d'alcools dans des quantités de 66% en poids à 125% en poids.
  6. Procédé selon au moins une des revendications 1 à 5, caractérisé en ce que la cristallisation intervient à partir de la solution alcoolique.
  7. Procédé selon la revendication 6, caractérisé en ce que l'alcool utilisé est l'isobutanol.
  8. Procédé selon au moins l'une des revendications 1 à 7, caractérisé en ce que la phase organique mise en oeuvre est introduite dans le cycle en continu.
EP00983239A 1999-12-20 2000-12-07 Procede de production de phenolates de phosphonium Expired - Lifetime EP1242347B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19961520 1999-12-20
DE19961520A DE19961520A1 (de) 1999-12-20 1999-12-20 Verfahren zur Herstellung von Phosphoniumphenolaten
PCT/EP2000/012325 WO2001046100A1 (fr) 1999-12-20 2000-12-07 Procede de production de phenolates de phosphonium

Publications (2)

Publication Number Publication Date
EP1242347A1 EP1242347A1 (fr) 2002-09-25
EP1242347B1 true EP1242347B1 (fr) 2004-10-13

Family

ID=7933456

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00983239A Expired - Lifetime EP1242347B1 (fr) 1999-12-20 2000-12-07 Procede de production de phenolates de phosphonium

Country Status (12)

Country Link
US (1) US6710153B2 (fr)
EP (1) EP1242347B1 (fr)
JP (1) JP4856340B2 (fr)
KR (1) KR20020062354A (fr)
CN (1) CN1211389C (fr)
AT (1) ATE279385T1 (fr)
AU (1) AU2005901A (fr)
BR (1) BR0016559A (fr)
DE (2) DE19961520A1 (fr)
ES (1) ES2231294T3 (fr)
TW (1) TWI233439B (fr)
WO (1) WO2001046100A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10164144A1 (de) 2001-12-27 2003-07-10 Bayer Ag Verfahren zur Herstellung von Quartärsalzphenolatlösungen und zur Regenerierung und Rückführung von Quartärsalzphenolatlösungen aus Reaktionsgemischen
DE10215498A1 (de) * 2002-04-09 2003-10-23 Bayer Ag Lagerung von Phosphoniumphenolat-Katalysatoren und deren Verwendung als Umesterungskatalysatoren
DE10219027A1 (de) * 2002-04-29 2003-11-06 Bayer Ag Verfahren zur Herstellung einer flüssigen Formulierung von Phosphoniumphenolaten
US10413349B2 (en) * 2011-03-04 2019-09-17 Covidien Lp System and methods for identifying tissue and vessels
JP6666193B2 (ja) * 2015-04-22 2020-03-13 国立大学法人名古屋大学 エステル交換反応用触媒及びそれを用いたエステル化合物の製造方法
CN113307827A (zh) * 2021-06-04 2021-08-27 山东师范大学实验厂 一种四苯基膦苯酚盐的水相合成方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02246140A (ja) * 1989-03-17 1990-10-01 Nitto Denko Corp 半導体装置
JPH0340459A (ja) * 1989-07-07 1991-02-21 Nitto Denko Corp 半導体装置
JP3117296B2 (ja) * 1992-09-17 2000-12-11 三井化学株式会社 フェノール類の選択的パラ位カルボキシル化方法
EP0826693A1 (fr) 1996-09-03 1998-03-04 Bayer Ag Procédé de préparation de phénolates de phosphonium
DE19727351C1 (de) 1997-06-27 1999-02-11 Bayer Ag Verfahren zur Herstellung von Phosphoniumphenolaten

Also Published As

Publication number Publication date
KR20020062354A (ko) 2002-07-25
CN1411428A (zh) 2003-04-16
ES2231294T3 (es) 2005-05-16
EP1242347A1 (fr) 2002-09-25
DE19961520A1 (de) 2001-06-21
AU2005901A (en) 2001-07-03
US6710153B2 (en) 2004-03-23
DE50008270D1 (de) 2004-11-18
CN1211389C (zh) 2005-07-20
ATE279385T1 (de) 2004-10-15
BR0016559A (pt) 2002-09-10
TWI233439B (en) 2005-06-01
JP2003518046A (ja) 2003-06-03
WO2001046100A1 (fr) 2001-06-28
US20030013837A1 (en) 2003-01-16
JP4856340B2 (ja) 2012-01-18

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